Synthesis and Characterization of a Metallacyclic Framework with Three Fused Five-membered Rings

Congqing Zhu; Jingjing Wu; Shenyan Li; Yuhui Yang; Jun Zhu; Xin Lu; Haiping Xia

doi:10.1002/anie.201704057

Synthesis and Characterization of a Metallacyclic Framework with Three Fused Five-membered Rings

Angew Chem Int Ed Engl. 2017 Jul 24;56(31):9067-9071. doi: 10.1002/anie.201704057.

Authors

Congqing Zhu^{1

2}, Jingjing Wu¹, Shenyan Li¹, Yuhui Yang¹, Jun Zhu¹, Xin Lu¹, Haiping Xia¹

Affiliations

¹ State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center of Chemistry for Energy Materials (iChEM), Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.
² State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210093, China.

PMID: 28586168
DOI: 10.1002/anie.201704057

Abstract

Polycyclic complexes containing a bridgehead transition metal are interesting species because the transition metal is shared by all the rings simultaneously. In this study, we present a novel osmium-bridgehead system with three fused five-membered rings. This novel framework can be viewed as a 10-atom carbon chain coordinating to the osmium center. In sharp contrast to the nonplanar organic analogue, this unique metallacycle exhibits good planarity, which was unambiguously verified by means of X-ray diffraction. Interestingly, preliminary DFT calculations show that the aromaticity in the three 5MRs of these osmatricycles can be easily tuned by the ligand substitution. Finally, the broad UV/Vis absorption spectra of these novel polycyclic complexes were also reported.

Keywords: DFT calculations; aromaticity; metallacycles; metallapentalene; osmium.

Publication types

Research Support, Non-U.S. Gov't